EP2791080B1 - Part made of cmc - Google Patents

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EP2791080B1
EP2791080B1 EP12806552.1A EP12806552A EP2791080B1 EP 2791080 B1 EP2791080 B1 EP 2791080B1 EP 12806552 A EP12806552 A EP 12806552A EP 2791080 B1 EP2791080 B1 EP 2791080B1
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interphase
matrix
layer
ceramic
elementary
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German (de)
French (fr)
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EP2791080A1 (en
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Franck Lamouroux
Sébastien BERTRAND
Sylvain JACQUES
Caroline LOUCHET
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Centre National de la Recherche Scientifique CNRS
Safran Ceramics SA
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Centre National de la Recherche Scientifique CNRS
Safran Ceramics SA
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
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    • C04B2235/74Physical characteristics
    • C04B2235/78Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/781Nanograined materials, i.e. having grain sizes below 100 nm
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    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material

Definitions

  • the invention relates to ceramic matrix or CMC composite material parts.
  • piece of CMC material is meant here a piece of a material comprising a fibrous reinforcement carbon fiber or ceramic densified by a matrix at least predominantly ceramic.
  • CMC materials are used in various applications, particularly in the aeronautical and space fields, where their thermostructural properties are exploited, that is to say their ability to form structural elements because of their mechanical strength, particularly in bending, in traction and impact, much higher than that of massive ceramics, and their ability to maintain this mechanical strength up to high temperatures well above 1000 ° C.
  • a first known approach to improve the oxidation resistance consists in performing a sequenced interphase by alternating nanometric layers of crack-deflecting material, such as PyC or BN, with nanometric layers of material having a function of protection against oxidation.
  • a material such as silicon carbide (SiC) or a ternary Si-BC capable of forming, in the presence of oxygen, a vitreous compound that can heal cracks by passing to the pasty state at the high temperatures at which the CMC material is exposed .
  • Forming P-CVI interphase sequenced type (PyC-SiC) n is as described in the documents of Sébastien BERTRAND AND AL. : "Influence of strong fiber / coating interfaces on the mechanical behavior and viability of Hi-Nicalon / (PyC-SiC) n / SiC minicomposites", Journal of the American Ceramic Society, Blackwell Publishing, MALDEN, MA, US, vol. 84, No. 4, April 1, 2011 (2001-04-01), pages 787-794 , and of Roger NASLAIN AND AL. : Trans Engineering Publications Ltd., STAFA-ZURICH, CH, Vol. 159-160, January 1, 1999 (1999-01-01), pages 359-365 .
  • the composites presented are mini-composites or micro-composites with unidirectional reinforcement.
  • a second known approach consists of incorporating into the matrix one or more phases in a material capable of conferring self-healing properties on the matrix in order to avoid or slow down the propagation of cracks in the matrix, such phases being in particular B 4 C boron carbide or a ternary Si-BC system.
  • phases being in particular B 4 C boron carbide or a ternary Si-BC system.
  • a third known approach consists in producing a sequential matrix comprising layers of material deviating from cracks, for example PyC or BN, alternating with layers of ceramic material, the deflection of cracks within the matrix delaying access to a medium ambient oxidant with interphase or fibers.
  • a fourth known approach consists of making a PyC or BN interphase little anisotropic to allow a strong bond with a matrix or a ceramic matrix layer, in particular SiC, so that the shear strengths within the interphase layer and at the fiber-interphase and interphase-matrix linkages are greater than those encountered within the matrix.
  • the invention provides a SiC matrix composite material comprising a fibrous reinforcement of SiC fibers coated with a coating comprising PyC or SiC.
  • interphase coating having, on its outer surface, ceramic grains whose size is substantially between 20 nanometers and 200 nanometers, with presence of grains larger than 50 nanometers.
  • the object of the invention is to provide a part made of CMC material having an improved lifetime, especially during exposure under load in an oxidizing medium at a high temperature.
  • the attachment of the sequenced matrix on the interphase coating promotes the charge transfer between the matrix and the fibers, which is important from the point of view of the mechanical strength of the part and its service life in an oxidizing environment.
  • the bond between the interphase coating and the matrix has a higher shear strength than those encountered within the matrix.
  • the damage by cracking is reported within the sequenced matrix and not in a privileged manner at the interphase. Due to the sequencing of the matrix, this damage occurs by a combination of mode I (transversely propagating cracking in a ceramic matrix layer) and mode II (cracking propagating along a layer of crack-deflecting material) , which delays the exposure of the interphase coating to oxygen from the ambient medium via the cracking network. The service life of the part is thus increased.
  • the matrix layer located closest to the interphase coating is a PyC or BC crack-deflecting material layer.
  • the interphase coating is formed of first elemental layers of boron-doped carbon alternating with second ceramic elemental layers and the atomic percentage of boron is between 5% and 20% in each first elemental layer, each second elemental layer of the coating. interphase being made of silicon carbide.
  • Each first elemental layer of the interphase coating may have an average thickness of between 20 nanometers and 500 nanometers.
  • Each second elemental layer of the interphase coating may have an average thickness of between 20 nanometers and 500 nanometers.
  • the average total thickness of the interphase coating may be between 0.10 micrometers and 4 micrometers, in average value.
  • the invention is also directed to a method according to claim 5.
  • Each first elemental layer of the interphase coating is formed from a gas phase in which the carbon precursor is propane.
  • the patent further discloses a method in which the or each first elemental layer of the interphase coating is formed from a gaseous phase in which the carbon precursor is methane or natural gas, the first elemental layer being carbon only .
  • the fibrous preform is consolidated by the interphase coating, that is to say that the interphase coating binds the fibers of the preform so that the preform is rigid enough to be handled while retaining its shape without the assistance of a maintenance tool.
  • a first step of producing a piece of CMC material according to the invention consists in producing a fiber preform intended to form the fibrous reinforcement of the part to be produced and therefore having a shape corresponding to that of this part.
  • the preform is made of carbon or ceramic fibers, the fibers being for example based on silicon carbide SiC when it comes to ceramic fibers.
  • Preforms can be made from unidimensional fibrous structures such as wires, cables or wicks, for example by filament winding or multilayer weaving (or three-dimensional weaving) possibly followed by a shaping step.
  • two-dimensional fibrous structures such as two-dimensional fabrics or sheets of yarns or cables to form layers which are draped over a shape and possibly linked together, for example by needling, stitching or thread implantation.
  • a complex shape preform can be made by assembling, for example by sewing, the different preform parts.
  • the preform can be made of fibers in a carbon precursor polymer or ceramic, with subsequent conversion of the precursor carbon or ceramic by heat treatment.
  • a second step is to form on the fibers of the preform an interphase coating with the preform generally maintained in its shape by means of a tool.
  • the interphase coating is a multilayer coating formed by conventional chemical vapor infiltration (CVI) process ("Chemical Vapor Infiltration").
  • CVI processes are well known. They consist in placing a porous preform in an enclosure in which a reaction gas phase is admitted which, under conditions including temperature and pressure, diffuse within the porosity of the preform to form, in contact therewith, a deposit of the desired material by decomposition of one or more components of the gas phase or by reaction between several constituents of the -this.
  • the interphase coating is formed of first elemental layers of boron-doped carbon alternating with second elemental ceramic layers, each second elementary layer of the interphase coating being silicon carbide.
  • a first elemental layer of the interphase coating formed solely of carbon is a pyrolytic carbon (PyC) layer formed by CVI in which the carbon precursor contained in the reaction gas phase is methane or gas natural.
  • PyC pyrolytic carbon
  • the patent still describes an interphase coating formed by a single sequence consisting of an elementary layer of PyC surmounted by a ceramic elemental layer.
  • a first elemental layer of the interphase coating formed of boron doped carbon (BC) is advantageously a layer formed by CVI in which the gaseous carbon precursor contained in the reaction gas phase is propane.
  • the gaseous precursor of boron contained in the gaseous phase is, for example, boron trichloride BCl 3 .
  • the respective proportions of carbon precursor and boron precursor in the reaction gas phase are chosen so as to have an atomic percentage of boron between 5% and 20% in the BC layer.
  • the interphase coating is multi-sequenced, i.e. formed by a plurality of first elementary layers BC alternating with a plurality of second silicon carbide elementary layers.
  • the boron-doped carbon of each first interphase elementary layer is advantageously PyC of smooth or rough laminar microstructure with an extinction angle of greater than 12 °, the type of microstructure being observable by illumination under polarized light, in particular appearing patterns in the form of "Maltese cross" and the extinction angle being the angle of rotation of polarization causing the extinction of the pattern, as is well known.
  • Each second ceramic elemental layer is a SiC silicon carbide layer.
  • an SiC layer may be formed by CVI using a gaseous phase containing a mixture of methyltrichlorosilane (MTS) and hydrogen gas H 2 .
  • MTS methyltrichlorosilane
  • the interphase coating is formed so that the last formed elementary layer is a ceramic layer whose outer surface is formed of ceramic grains having a size of substantially between 20 nanometers and 200 nanometers with presence grains larger than 50 nanometers, giving this surface a relatively high roughness so as to allow mechanical attachment of the first matrix layer.
  • size of ceramic grains essentially between 20 nanometers and 200 nanometers is meant here that more than 80% of the ceramic grains have a size in this range.
  • the presence of grains larger than 50 nanometers should preferably be significant, that is to say represent at least 20% of the ceramic layer.
  • the average thickness of each first elemental layer of boron-doped carbon interphase is preferably between 20 nanometers and 500 nanometers.
  • each second silicon carbide interphase elemental layer is preferably between 20 nanometers and 500 nanometers.
  • the average total thickness of the interphase coating is preferably between 0.10 micrometers and 4 micrometers, in average value.
  • This total thickness can be chosen so as to ensure the consolidation of the fiber preform by the single interphase coating, that is to say with an interphase coating bonding together the fibers of the preform sufficiently to have a stiffened preform manipulated while retaining its shape without the assistance of a holding tool.
  • the fiber preform Before forming the interphase coating and to promote a good attachment of this coating on the fibers, the fiber preform can be heat treated as described in document US 5,476,685 when it is made of carbon fiber or chemically treated as described in the document US 5,071,679 when it is made of ceramic fibers, in particular SiC or essentially SiC.
  • the preform provided with the interphase coating is then densified by a predominantly ceramic sequenced matrix comprising ceramic layers alternating with layers of material deviating from cracks.
  • the layers of crack-deflecting material may be made of pyrolytic carbon, optionally doped with boron or boron nitride BN.
  • the ceramic layers may be SiC or a ternary system Si-BC or boron carbide B 4 C.
  • a refractory material such as SiC
  • a self-healing type material such as Si -BC or B 4 C.
  • Self-healing material means a material capable of generating a vitreous phase by oxidation, thus achieving healing by crack filling.
  • the sequenced matrix can be obtained by CVI. Methods of producing sequenced matrices are described in particular in the documents US 5,965,266 and US 6,068,930 already mentioned.
  • a sequential matrix comprising layers of ceramic material is particularly advantageous in that by combining a mode of cracking transverse to the ceramic layers with a mode of cracking parallel to the layers of material deflecting crack, it delays the exposure of the carbon from the interphase to the oxygen of the ambient medium via the cracking network.
  • the matrix layer formed first (closest to the interphase coating) is a layer of PyC or BC crack deflector material.
  • the relatively high roughness of the outer surface of the last formed interphase coating elemental layer allows a mechanical interlock between the interphase coating and the matrix advantageously avoiding that under the effect of constraints decohesion occurs preferentially at this level, creating a passage for oxygen from the ambient to the carbon of the interphase coating.
  • the shear strength of the first layer of the crack-deflecting material matrix is greater than that otherwise existing within the matrix.
  • this contributes to improving the life of the CMC material by preserving the integrity of the interphase.
  • this mechanical coupling between the interphase coating and the matrix contributes to ensuring a good charge transfer from the matrix to the fibers, which is essential for the mechanical properties of the CMC material.
  • Example 1 C-fibers, interphase (BC propane / SiC) x4, PyC matrix-type, B 4 C, SiC, Si-BC) (Invention)
  • Fibrous preforms were obtained from a fabric made by multilayer weaving of carbon threads. The weaving was performed with interlock type weave so as to increase the delamination resistance of the finally obtained material. Preforms were obtained by cutting into the multilayer fabric obtained and held between two perforated plates of a graphite shaper, so as to have a volume content of fibers generally of between approximately 30% and 50% (i.e. say the percentage of the apparent volume of the preform occupied by the fibers).
  • An interphase coating formed of layers of boron-doped pyrolytic carbon alternating with SiC layers was made by conventional CVI on the fibers of the preforms.
  • the coating formed of 4 bi-layers BC / SiC is called (BC / SiC) x4.
  • each elemental layer of BC was carried out with a gaseous reaction phase containing a mixture of C 3 H 8 propane and boron trichloride BCl 3 so as to obtain a BC material.
  • each elemental layer of SiC was carried out with a reaction gas phase containing a mixture of MTS and H 2 .
  • each elemental layer was chosen to obtain average thicknesses of the order of 50 nanometers and 100 nanometers, respectively for the BC and SiC layers, giving an average thickness of consolidating interphase of about 0.6 micrometers. It should however be noted that these thicknesses vary greatly depending in particular on the location relative to the holes of the perforated plates of the graphite shaper, the proximity of a hole favoring the access of the reaction gas phase, therefore the formation of a thicker layer.
  • the preforms consolidated by this coating were removed from their holding tool and densified by CVI by a predominantly ceramic matrix consisting of layers of pyrolytic carbon PyC alternating with layers of boron carbide B 4 C or silicon carbide SiC or mixed carbide boron and silicon forming a ternary system Si-BC, the layers thus forming the following sequence (starting from the matrix layer closest to the interphase): C / B 4 C / C / SiC / C / Si-BC / C / SiC (which can be repeated one or more times) the crack-deflecting material C phases being made of pyrolytic carbon derived from a precursor formed of a mixture of propane and natural gas, the refractory ceramic SiC phases and the self-healing ceramics Si-BC and B 4 C phases being obtained as described in the document US 5,965,266 supra.
  • the roughness of the outer surface of the last formed interphase coating SiC layer appears on the Figures 1, 2 and 3 which are microscopic views of the interphase coating in the consolidation stage, before further densification, respectively in cross section, in longitudinal section and at the surface.
  • This roughness The formation of this SiC layer by grains of relatively large average size, here greater than 50 nanometers, thus with significant presence of grains larger than 50 nanometers.
  • Example 2 C-fibers, interphase (BC propane / SiC) x4, BC type matrix, B 4 C, SiC, Si-BC) (according to the invention)
  • Example 2 The procedure was as in Example 1 except for the sequential matrix in which the PyC pyrolytic carbon of the deflector layers of cracks is replaced by BC boron-doped carbon of a nature similar to that of the interphase coating.
  • Example 3 C-fibers, PyC CH interphase 4 / SiC, matrix type PyC, B 4 C, SiC, Si-BC (outside the invention)
  • Example 2 The procedure was as in Example 1 except for the interphase coating which was of PyC / SiC type formed of an elementary layer of PyC coated with an elemental layer of SiC.
  • the elemental layer of PyC was obtained by conventional CVI with a gas phase in which the carbon precursor was natural gas, namely essentially methane.
  • the average thicknesses targeted for the PyC and SiC layers were respectively of the order of 100 nanometers and 1 micron, sufficient to consolidate the preforms.
  • the figure 4 shows that the elementary layer of SiC has a relatively high surface roughness generated by the presence of coarse SiC grains larger than 50.
  • Example 4 (comparative) (C-fibers, BC / B 4 C / BC / SiC interphase, BC type matrix, B 4 C, SiC, Si-BC)
  • Example 2 The procedure was as in Example 2 except for the interphase coating which was of BC / B 4 C / BC / SiC type, the elementary layers of BC and the elementary layer of SiC being obtained as in Example 2 and the elementary layer of B 4 C being obtained as for the matrix.
  • the figure 5 shows that the outer surface of the SiC layer of the interphase coating is relatively smooth.
  • Example 5 (comparative) (C-fibers, interphase (BC nat / SiC gas ) x4, BC type matrix, B 4 C, SiC, Si-BC)
  • the Figures 6, 7 and 8 show that the interphase coating layer formed last (respectively in cross section, in longitudinal section and at the surface) is formed of SiC grains of relatively small average size and joined, not conferring significant roughness.
  • Example 6 (Comparative) (C-fibers, interphase (PYC CH 4 - C 3 H 8 / SiC) x2, PyC matrix-type, B 4 C, SiC, Si-BC)
  • Example 3 The procedure was as in Example 3 except for the interphase coating which was of the (PyC / SiC) x 2 type formed of two PyC layers alternating with two layers of SiC and with elementary layers of PyC obtained by CVI. conventional with a gas phase in which the PyC precursor was a mixture of propane and natural gas, propane being the main precursor.
  • the interphase coating which was of the (PyC / SiC) x 2 type formed of two PyC layers alternating with two layers of SiC and with elementary layers of PyC obtained by CVI. conventional with a gas phase in which the PyC precursor was a mixture of propane and natural gas, propane being the main precursor.
  • the overall thickness of the interphase was chosen to be similar to that of Example 3, sufficient to consolidate the preforms.
  • the figure 9 shows that the outer elemental layer of PyC has a low roughness, the SiC grains being of relatively small size and joined.
  • Curves A, B and C of the figure 10 show the relationship between tensile stress and relative elongation for parts of Examples 1, 3 and 6, respectively, to failure.
  • the linear shape of the curve C over most of it, until failure, reflects a decohesion between interphase coating and matrix, hence a lower charge transfer between matrix and fibers.
  • Parts obtained according to Examples 1, 3 and 6 were also subjected to cyclic fatigue life tests at 600 ° C. and 1200 ° C. in air, these tests consisting in subjecting the parts to a tensile stress of 120.degree. MPa (in apparent stress) with a stress relaxation frequency of 0.25 Hz.
  • the service life of the parts obtained according to Examples 1 and 3 is much greater than that of the part obtained according to Example 6 at 600 ° C. At 1200 ° C, the service life of the part obtained according to Example 3 is the lowest, this being explained by the greater sensitivity to oxidation of PyC obtained from a natural gas precursor.
  • Parts according to Examples 2 and 5 were subjected to cyclic fatigue life tests at 600 ° C under the same conditions as indicated above except for the applied stress which was 90 MPa or 130 MPa.
  • the foregoing examples show that a surface roughness of the ceramic elemental layer formed last in the interphase coating capable of ensuring an effective mechanical coupling with the matrix can be obtained by performing the interphase coating under conditions favoring in this last layer, a growth of ceramic grains rather than their germination, then that conditions favoring germination rather than growth generate relatively small and close grains whose growth is quickly blocked by their proximity.

Description

Arrière-plan de l'inventionBackground of the invention

L'invention concerne des pièces en matériau composite à matrice céramique ou CMC.The invention relates to ceramic matrix or CMC composite material parts.

Par pièce en matériau CMC, on entend ici une pièce en un matériau comprenant un renfort fibreux en fibres de carbone ou de céramique densifié par une matrice au moins majoritairement en céramique.By piece of CMC material is meant here a piece of a material comprising a fibrous reinforcement carbon fiber or ceramic densified by a matrix at least predominantly ceramic.

Les matériaux CMC sont utilisés dans diverses applications, notamment dans les domaines aéronautique et spatial, où sont exploitées leurs propriétés thermostructurales, c'est-à-dire leur capacité à constituer des éléments de structure en raison de leur tenue mécanique, notamment en flexion, en traction et aux chocs, bien supérieure à celle des céramiques massives, et leur capacité à conserver cette tenue mécanique jusqu'à des températures élevées bien supérieures à 1 000°C.CMC materials are used in various applications, particularly in the aeronautical and space fields, where their thermostructural properties are exploited, that is to say their ability to form structural elements because of their mechanical strength, particularly in bending, in traction and impact, much higher than that of massive ceramics, and their ability to maintain this mechanical strength up to high temperatures well above 1000 ° C.

Dans les matériaux CMC, la fissuration de la matrice est en pratique inévitable, souvent dès la fabrication.In CMC materials, die cracking is in practice inevitable, often from the moment of manufacture.

Il a été proposé d'interposer entre les fibres et la matrice un revêtement d'interphase qui est capable d'assurer un transfert de charges efficace entre la matrice et les fibres et qui est en un matériau capable de dévier des fissures parvenant au revêtement d'interphase pour éviter que des fissures se propageant dans la matrice atteignent les fibres du renfort et provoquent la rupture de celles-ci, dégradant rapidement les propriétés mécaniques du matériau CMC. Les documents US 4 752 503 et US 5 026 604 divulguent la réalisation d'une interphase en carbone pyrolytique (PyC) ou nitrure de bore (BN) ayant une structure lamellaire ou en feuillets. La réalisation d'une interphase déviatrice de fissure en matériau poreux est également connue.It has been proposed to interpose between the fibers and the matrix an interphase coating which is capable of providing efficient charge transfer between the matrix and the fibers and which is of a material capable of deflecting cracks to the coating of the matrix. interphase to prevent cracks propagating in the matrix reach the fibers of the reinforcement and cause the rupture thereof, rapidly degrading the mechanical properties of the CMC material. The documents US 4,752,503 and US 5,026,604 disclose carrying out an interphase of pyrolytic carbon (PyC) or boron nitride (BN) having a lamellar or flake structure. The realization of a deflection interphase crack of porous material is also known.

Toutefois, dans des conditions d'utilisation sous atmosphère oxydante et à température élevée, la propagation des fissures jusqu'à l'interphase offre des voies d'accès à l'oxygène, et il se produit alors une oxydation de l'interphase PyC ou BN, voire des fibres sous-jacentes lorsqu'elles sont en carbone, conduisant à une dégradation du matériau CMC.However, under conditions of use in an oxidizing atmosphere and at a high temperature, the propagation of cracks up to the interphase provides oxygen access routes, and then the PyC interphase is oxidized or BN, or even underlying fibers when they are carbon, leading to degradation of the CMC material.

Une première approche connue pour améliorer la tenue à l'oxydation consiste à réaliser une interphase séquencée en alternant des couches nanométriques en matériau déviateur de fissures, tel que PyC ou BN, avec des couches nanométriques en matériau ayant une fonction de protection contre l'oxydation, notamment un matériau tel que du carbure de silicium (SiC) ou un ternaire Si-B-C capable de former en présence d'oxygène un composé vitreux pouvant cicatriser des fissures par passage à l'état pâteux aux hautes températures auxquelles le matériau CMC est exposé. On pourra se référer au document US 5 738 951 qui décrit, pour un matériau composite à matrice SiC, la formation d'une telle interphase séquencée par infiltration chimique en phase gazeuse en mode pulsé, ou P-CVI (pour "Pulsed-Chemical Vapour Infiltration"), les couches élémentaires de l'interphase ayant une épaisseur inférieure à 10 nm.A first known approach to improve the oxidation resistance consists in performing a sequenced interphase by alternating nanometric layers of crack-deflecting material, such as PyC or BN, with nanometric layers of material having a function of protection against oxidation. , in particular a material such as silicon carbide (SiC) or a ternary Si-BC capable of forming, in the presence of oxygen, a vitreous compound that can heal cracks by passing to the pasty state at the high temperatures at which the CMC material is exposed . We can refer to the document US 5,738,951 which describes, for an SiC matrix composite material, the formation of such a sequenced interphase by pulsed-mode gas-phase chemical infiltration, or P-CVI (for "Pulsed-Chemical Vapor Infiltration"), the elementary layers of the interphase having a thickness of less than 10 nm.

La formation par P-CVI d'interphases séquencées de type (PyC-SiC)n est décrite aussi dans les documents de Sébastien BERTRAND ET AL. : "Influence of strong fiber/coating interfaces on the mechanical behavior and lifetime of Hi-Nicalon/(PyC-SiC)n/SiC minicomposites", Journal of the American Ceramic Society, Blackwell Publishing, MALDEN, MA, US, vol. 84, N° 4, 1er avril 2011 (2001-04-01), pages 787-794 , et de Roger NASLAIN ET AL. : "Processing of ceramic matrix composites by pulsed-CVI and related techniques", Key Engineering Materials, Trans Tech Publications Ltd., STAFA-ZURICH, CH, Vol. 159-160, 1er janvier 1999 (1999-01-01), pages 359-365 .Forming P-CVI interphase sequenced type (PyC-SiC) n is as described in the documents of Sébastien BERTRAND AND AL. : "Influence of strong fiber / coating interfaces on the mechanical behavior and viability of Hi-Nicalon / (PyC-SiC) n / SiC minicomposites", Journal of the American Ceramic Society, Blackwell Publishing, MALDEN, MA, US, vol. 84, No. 4, April 1, 2011 (2001-04-01), pages 787-794 , and of Roger NASLAIN AND AL. : Trans Engineering Publications Ltd., STAFA-ZURICH, CH, Vol. 159-160, January 1, 1999 (1999-01-01), pages 359-365 .

Dans ces deux documents, les composites présentés sont des mini-composites ou micro-composites à renfort unidirectionnel.In these two documents, the composites presented are mini-composites or micro-composites with unidirectional reinforcement.

Le document de Takashi NOZAWA ET AL. : "Tensile, flexural, and shear properties of neutron irradiated SiC/SiC composites with différent fiber-matrix interfaces", STP/ASTM International, ASTM International, WEST CONSHOHOCKEN, PA., 2001, US, Vol. 1475 STP, 1er janvier 2004 (2004-01-01), pages 392-404 , mentionne aussi des mini-composites à renfort fibreux unidirectionnel et matrice SiC, avec interphase de type (SiC-PyC)n, les composites ayant été réalisés par processus CVI isotherme, sans autre précision.The document Takashi NOZAWA AND AL. : "Tensile, flexural, and shear properties of irradiated neutron SiC / SiC composites with different fiber-matrix interfaces", STP / ASTM International, ASTM International, WEST CONSHOHOCKEN, PA., 2001, US, Vol. 1475 STP, January 1, 2004 (2004-01-01), pages 392-404 , also mentions unidirectional fiber-reinforced mini-composites and SiC matrix, with interphase type (SiC-PyC) n , the composites having been made by isothermal CVI process, without further precision.

Une deuxième approche connue consiste à incorporer à la matrice une ou plusieurs phases en un matériau capable de conférer des propriétés auto-cicatrisantes à la matrice afin d'éviter ou ralentir la propagation de fissures au sein de la matrice, de telles phases étant notamment en carbure de bore B4C ou en un système ternaire Si-B-C. On pourra se référer au document US 5 965 266 qui décrit une matrice comprenant des phases en SiC alternant avec des phases B4C ou Si-B-C.A second known approach consists of incorporating into the matrix one or more phases in a material capable of conferring self-healing properties on the matrix in order to avoid or slow down the propagation of cracks in the matrix, such phases being in particular B 4 C boron carbide or a ternary Si-BC system. We can refer to the document US 5,965,266 which describes a matrix comprising alternating SiC phases with B 4 C or Si-BC phases.

Une troisième approche connue consiste à réaliser une matrice séquencée comprenant des couches en matériau déviateur de fissures, par exemple PyC ou BN, alternant avec des couches en matériau céramique, la déviation des fissures au sein de la matrice retardant l'accès d'un milieu oxydant ambiant à l'interphase ou aux fibres. On pourra se référer au document US 6 068 930 .A third known approach consists in producing a sequential matrix comprising layers of material deviating from cracks, for example PyC or BN, alternating with layers of ceramic material, the deflection of cracks within the matrix delaying access to a medium ambient oxidant with interphase or fibers. We can refer to the document US 6,068,930 .

Une quatrième approche connue consiste à réaliser une interphase PyC ou BN peu anisotrope pour permettre une liaison forte avec une matrice ou une couche de matrice céramique, notamment SiC, de sorte que les résistances à la rupture par cisaillement au sein de la couche d'interphase et au niveau des liaisons fibres-interphase et interphase-matrice sont supérieures à celles rencontrées au sein de la matrice.A fourth known approach consists of making a PyC or BN interphase little anisotropic to allow a strong bond with a matrix or a ceramic matrix layer, in particular SiC, so that the shear strengths within the interphase layer and at the fiber-interphase and interphase-matrix linkages are greater than those encountered within the matrix.

On connait en outre la publication Hinoki et al. (« The effect of neutron-irradiation on the shear properties of SiC/SiC composites with varied interface") qui divulgue une pièce en matériau composite à matrice SiC comprenant un renfort fibreux de fibres de SiC revêtu par un revêtement comprenant du PyC ou SiC. Il n'est pas décrit de revêtement d'interphase présentant, sur sa surface externe, des grains céramique dont la taille est comprise essentiellement entre 20 nanomètres et 200 nanomètres, avec présence de grains de taille supérieure à 50 nanomètres.In addition, the publication Hinoki et al. The invention provides a SiC matrix composite material comprising a fibrous reinforcement of SiC fibers coated with a coating comprising PyC or SiC. There is no disclosure of interphase coating having, on its outer surface, ceramic grains whose size is substantially between 20 nanometers and 200 nanometers, with presence of grains larger than 50 nanometers.

On connait en outre le document US 5 284 685 qui divulgue une pièce en matériau composite à matrice de carbone dopé par du SiC. Les fibres du renfort sont revêtues par un revêtement PyC/SiC puis la préforme est densifiée par la matrice de carbone dopé SiC. L'emploi de méthane est indiqué pour former le PyC. On ne retrouve toutefois pas de matrice séquencée majoritairement en céramique comportant des couches de matrice en matériau déviateur de fissure alternant avec des couches de matrice en matériau céramique, ni de revêtement d'interphase formé de couches en carbone dopé au bore alternant avec des couches en SiC.We also know the document US 5,284,685 which discloses a piece of carbon matrix composite material doped with SiC. The fibers of the reinforcement are coated with a PyC / SiC coating and the preform is densified by the SiC doped carbon matrix. The use of methane is indicated to form PyC. However, there is no predominantly ceramic-based matrix with matrix layers of crack-deflecting material alternating with matrix layers of ceramic material, nor interphase coating formed of boron-doped carbon layers alternating with layers of ceramic material. SiC.

Objet et résumé de l'inventionObject and summary of the invention

L'invention a pour but de proposer une pièce en matériau CMC ayant une durée de vie améliorée, notamment lors d'exposition sous charge en milieu oxydant à température élevée.The object of the invention is to provide a part made of CMC material having an improved lifetime, especially during exposure under load in an oxidizing medium at a high temperature.

Ce but est atteint grâce à une pièce selon la revendication 1.This object is achieved by means of a part according to claim 1.

L'accrochage de la matrice séquencée sur le revêtement d'interphase favorise le transfert de charge entre la matrice et les fibres, ce qui est important du point de vue de la tenue mécanique de la pièce et de sa durée de vie en environnement oxydant. De préférence, la liaison entre le revêtement d'interphase et la matrice présente une résistance à la rupture en cisaillement supérieure à celles rencontrées au sein de la matrice. Avantageusement, l'endommagement par fissuration est reporté au sein de la matrice séquencée et non pas de façon privilégiée au niveau de l'interphase. Du fait du séquençage de la matrice, cet endommagement se produit par une combinaison de mode I (fissuration se propageant transversalement dans une couche de matrice céramique) et de mode II (fissuration se propageant le long d'une couche en matériau déviateur de fissure), ce qui retarde l'exposition du revêtement d'interphase à l'oxygène du milieu ambiant via le réseau de fissuration. La durée de vie de la pièce est ainsi augmentée.The attachment of the sequenced matrix on the interphase coating promotes the charge transfer between the matrix and the fibers, which is important from the point of view of the mechanical strength of the part and its service life in an oxidizing environment. Preferably, the bond between the interphase coating and the matrix has a higher shear strength than those encountered within the matrix. Advantageously, the damage by cracking is reported within the sequenced matrix and not in a privileged manner at the interphase. Due to the sequencing of the matrix, this damage occurs by a combination of mode I (transversely propagating cracking in a ceramic matrix layer) and mode II (cracking propagating along a layer of crack-deflecting material) , which delays the exposure of the interphase coating to oxygen from the ambient medium via the cracking network. The service life of the part is thus increased.

La couche de matrice située au plus près du revêtement d'interphase est une couche en matériau déviateur de fissures PyC ou BC.The matrix layer located closest to the interphase coating is a PyC or BC crack-deflecting material layer.

Le revêtement d'interphase est formé de premières couches élémentaires en carbone dopé au bore alternant avec des deuxièmes couches élémentaires en céramique et le pourcentage atomique de bore est compris entre 5% et 20% dans chaque première couche élémentaire, chaque deuxième couche élémentaire du revêtement d'interphase étant en carbure de silicium.The interphase coating is formed of first elemental layers of boron-doped carbon alternating with second ceramic elemental layers and the atomic percentage of boron is between 5% and 20% in each first elemental layer, each second elemental layer of the coating. interphase being made of silicon carbide.

Chaque première couche élémentaire du revêtement d'interphase peut avoir une épaisseur moyenne comprise entre 20 nanomètres et 500 nanomètres.Each first elemental layer of the interphase coating may have an average thickness of between 20 nanometers and 500 nanometers.

Chaque deuxième couche élémentaire du revêtement d'interphase peut avoir une épaisseur moyenne comprise entre 20 nanomètres et 500 nanomètres.Each second elemental layer of the interphase coating may have an average thickness of between 20 nanometers and 500 nanometers.

L'épaisseur totale moyenne du revêtement d'interphase peut être comprise entre 0,10 micromètres et 4 micromètres, en valeur moyenne.The average total thickness of the interphase coating may be between 0.10 micrometers and 4 micrometers, in average value.

L'invention vise également un procédé selon la revendication 5.The invention is also directed to a method according to claim 5.

Chaque première couche élémentaire du revêtement d'interphase est formée à partir d'une phase gazeuse dans laquelle le précurseur de carbone est du propane.Each first elemental layer of the interphase coating is formed from a gas phase in which the carbon precursor is propane.

Le brevet décrit encore un procédé dans lequel la ou chaque première couche élémentaire du revêtement d'interphase est formée à partir d'une phase gazeuse dans laquelle le précurseur de carbone est du méthane ou du gaz naturel, la première couche élémentaire étant en carbone seul.The patent further discloses a method in which the or each first elemental layer of the interphase coating is formed from a gaseous phase in which the carbon precursor is methane or natural gas, the first elemental layer being carbon only .

Avantageusement, on réalise une consolidation de la préforme fibreuse par le revêtement d'interphase, c'est-à-dire que le revêtement d'interphase lie les fibres de la préforme de sorte que la préforme est suffisamment rigide pour pouvoir être manipulée en conservant sa forme sans l'assistance d'un outillage de maintien.Advantageously, the fibrous preform is consolidated by the interphase coating, that is to say that the interphase coating binds the fibers of the preform so that the preform is rigid enough to be handled while retaining its shape without the assistance of a maintenance tool.

Brève description des dessinsBrief description of the drawings

D'autres particularités et avantages de l'invention ressortiront à la lecture de la description faite ci-après, à titre indicatif mais non limitatif, en référence aux dessins annexés sur lesquels :

  • les figures 1 à 3 sont des vues au microscope montrant des revêtements d'interphases pour des pièces en matériau CMC conformes à l'invention ;
  • la figure 4 est une vue au microscope montrant un revêtement d'interphase pour une pièce en matériau CMC hors invention ;
  • les figures 5 à 9 sont des vues au microscope montrant des revêtements d'interphase de pièces en matériau CMC réalisées à titre comparatif ; et
  • la figure 10 montre des courbes représentant la relation entre contrainte en traction et déformation pour différentes pièces en matériau CMC.
Other features and advantages of the invention will become apparent on reading the description given below, by way of indication but not limitation, with reference to the accompanying drawings in which:
  • the Figures 1 to 3 are microscope views showing interphase coatings for parts made of CMC material according to the invention;
  • the figure 4 is a microscope view showing an interphase coating for a piece of CMC material outside the invention;
  • the Figures 5 to 9 are microscope views showing interphase coatings of CMC material parts made for comparison; and
  • the figure 10 shows curves representing the relationship between tensile stress and strain for different pieces of CMC material.

Description détaillée de l'inventionDetailed description of the invention

Une première étape de réalisation d'une pièce en matériau CMC conforme à l'invention consiste à réaliser une préforme fibreuse destinée à constituer le renfort fibreux de la pièce à réaliser et ayant donc une forme correspondant à celle de cette pièce.A first step of producing a piece of CMC material according to the invention consists in producing a fiber preform intended to form the fibrous reinforcement of the part to be produced and therefore having a shape corresponding to that of this part.

La préforme est réalisée en fibres de carbone ou de céramique, les fibres étant par exemple à base de carbure de silicium SiC lorsqu'il s'agit de fibres céramique.The preform is made of carbon or ceramic fibers, the fibers being for example based on silicon carbide SiC when it comes to ceramic fibers.

Divers procédés d'élaboration de préformes fibreuses sont bien connus.Various methods for producing fibrous preforms are well known.

Des préformes peuvent être réalisées à partir de structures fibreuses unidimensionnelles telles que des fils, câbles ou mèches, par exemple par enroulement filamentaire ou tissage multicouches (ou tissage tridimensionnel) éventuellement suivi d'une étape de mise en forme.Preforms can be made from unidimensional fibrous structures such as wires, cables or wicks, for example by filament winding or multilayer weaving (or three-dimensional weaving) possibly followed by a shaping step.

Il est possible aussi de partir de structures fibreuses bidimensionnelles telles que des tissus bidimensionnels ou des nappes de fils ou de câbles pour former des strates qui sont drapées sur une forme et éventuellement liées entre elles par exemple par aiguilletage, couture ou implantation de fils.It is also possible to start from two-dimensional fibrous structures such as two-dimensional fabrics or sheets of yarns or cables to form layers which are draped over a shape and possibly linked together, for example by needling, stitching or thread implantation.

Il est possible aussi de partir de structures fibreuses tridimensionnelles telles que des feutres.It is also possible to start from three-dimensional fibrous structures such as felts.

Dans tous les cas, une préforme de forme complexe peut être réalisée par assemblage, par exemple par couture, des différentes parties de préforme.In all cases, a complex shape preform can be made by assembling, for example by sewing, the different preform parts.

Dans tous les cas également, la préforme peut être réalisée en fibres en un polymère précurseur de carbone ou de céramique, avec transformation ultérieure du précurseur en carbone ou en céramique par traitement thermique.In all cases also, the preform can be made of fibers in a carbon precursor polymer or ceramic, with subsequent conversion of the precursor carbon or ceramic by heat treatment.

Une deuxième étape consiste à former sur les fibres de la préforme un revêtement d'interphase avec la préforme généralement maintenue dans sa forme au moyen d'un outillage. Le revêtement d'interphase est un revêtement multicouches formé par processus classique d'infiltration chimique en phase gazeuse ou CVI ("Chemical Vapor Infiltration"). Les processus CVI sont bien connus. Ils consistent à placer une préforme poreuse dans une enceinte dans laquelle est admise une phase gazeuse réactionnelle qui, dans des conditions notamment de température et de pression données, diffuse au sein de la porosité de la préforme pour former, au contact de celle-ci, un dépôt du matériau souhaité par décomposition d'un ou plusieurs constituants de la phase gazeuse ou par réaction entre plusieurs constituants de celle-ci.A second step is to form on the fibers of the preform an interphase coating with the preform generally maintained in its shape by means of a tool. The interphase coating is a multilayer coating formed by conventional chemical vapor infiltration (CVI) process ("Chemical Vapor Infiltration"). CVI processes are well known. They consist in placing a porous preform in an enclosure in which a reaction gas phase is admitted which, under conditions including temperature and pressure, diffuse within the porosity of the preform to form, in contact therewith, a deposit of the desired material by decomposition of one or more components of the gas phase or by reaction between several constituents of the -this.

De façon connue, dans un processus CVI classique, la phase gazeuse s'écoule de façon continue dans l'enceinte qui est maintenue à pression constante ou sensiblement constante (processus CVI isobare ou quasi-isobare).In a known manner, in a conventional CVI process, the gas phase flows continuously in the chamber which is maintained at constant or substantially constant pressure (isobaric or quasi-isobar CVI process).

Dans la présente invention, le revêtement d'interphase est formé de premières couches élémentaires en carbone dopé au bore alternant avec des deuxièmes couches élémentaires en céramique, chaque deuxième couche élémentaire du revêtement d'interphase étant en carbure de silicium.In the present invention, the interphase coating is formed of first elemental layers of boron-doped carbon alternating with second elemental ceramic layers, each second elementary layer of the interphase coating being silicon carbide.

Le brevet décrit encore le cas où une première couche élémentaire du revêtement d'interphase formée uniquement de carbone est une couche de carbone pyrolytique (PyC) formée par CVI dans laquelle le précurseur de carbone contenu dans la phase gazeuse réactionnelle est du méthane ou du gaz naturel.The patent further discloses the case where a first elemental layer of the interphase coating formed solely of carbon is a pyrolytic carbon (PyC) layer formed by CVI in which the carbon precursor contained in the reaction gas phase is methane or gas natural.

Dans le cas où la première couche élémentaire du revêtement d'interphase est formée uniquement de PyC, le brevet décrit encore un revêtement d'interphase formé par une seule séquence constituée par une couche élémentaire de PyC surmontée d'une couche élémentaire en céramique.In the case where the first elementary layer of the interphase coating is formed solely of PyC, the patent still describes an interphase coating formed by a single sequence consisting of an elementary layer of PyC surmounted by a ceramic elemental layer.

Une première couche élémentaire du revêtement d'interphase formée de carbone dopé au bore (BC) est avantageusement une couche formée par CVI dans laquelle le précurseur gazeux de carbone contenu dans la phase gazeuse réactionnelle est du propane. Le précurseur gazeux de bore contenu dans la phase gazeuse est par exemple du trichlorure de bore BCl3. Les proportions respectives de précurseur de carbone et de précurseur de bore dans la phase gazeuse réactionnelle sont choisies de manière à avoir un pourcentage atomique de bore entre 5% et 20% dans la couche BC.A first elemental layer of the interphase coating formed of boron doped carbon (BC) is advantageously a layer formed by CVI in which the gaseous carbon precursor contained in the reaction gas phase is propane. The gaseous precursor of boron contained in the gaseous phase is, for example, boron trichloride BCl 3 . The respective proportions of carbon precursor and boron precursor in the reaction gas phase are chosen so as to have an atomic percentage of boron between 5% and 20% in the BC layer.

Le revêtement d'interphase est multiséquencé, c'est-à-dire formé par une pluralité de premières couches élémentaires BC alternant avec une pluralité de deuxièmes couches élémentaires en carbure de silicium.The interphase coating is multi-sequenced, i.e. formed by a plurality of first elementary layers BC alternating with a plurality of second silicon carbide elementary layers.

Le carbone dopé au bore de chaque première couche élémentaire d'interphase est avantageusement du PyC de microstructure de type laminaire lisse ou rugueux avec un angle d'extinction supérieur à 12°, le type de microstructure étant observable par éclairage sous lumière polarisée faisant notamment apparaître des motifs en forme de "croix de Malte" et l'angle d'extinction étant l'angle de rotation de polarisation provoquant l'extinction du motif, comme cela est bien connu.The boron-doped carbon of each first interphase elementary layer is advantageously PyC of smooth or rough laminar microstructure with an extinction angle of greater than 12 °, the type of microstructure being observable by illumination under polarized light, in particular appearing patterns in the form of "Maltese cross" and the extinction angle being the angle of rotation of polarization causing the extinction of the pattern, as is well known.

Chaque deuxième couche élémentaire en céramique est une couche de carbure de silicium SiC.Each second ceramic elemental layer is a SiC silicon carbide layer.

Comme cela est bien connu, une couche en SiC peut être formée par CVI en utilisant une phase gazeuse contenant un mélange de méthyltrichlorosilane (MTS) et de gaz hydrogène H2.As is well known, an SiC layer may be formed by CVI using a gaseous phase containing a mixture of methyltrichlorosilane (MTS) and hydrogen gas H 2 .

Conformément à l'invention, le revêtement d'interphase est formé de sorte que la couche élémentaire formée en dernier est une couche en céramique dont la surface externe est formée de grains de céramique ayant une taille comprise essentiellement entre 20 nanomètres et 200 nanomètres avec présence de grains de taille supérieure à 50 nanomètres, conférant à cette surface une rugosité relativement forte de manière à permettre un accrochage mécanique de la première couche de matrice. Par taille de grains de céramique comprise essentiellement entre 20 nanomètres et 200 nanomètres, on entend ici que plus de 80% des grains de céramique ont une taille comprise dans cette plage. Par ailleurs, la présence de grains de taille supérieure à 50 nanomètres doit de préférence être significative, c'est-à-dire représenter au moins 20% de la couche en céramique.According to the invention, the interphase coating is formed so that the last formed elementary layer is a ceramic layer whose outer surface is formed of ceramic grains having a size of substantially between 20 nanometers and 200 nanometers with presence grains larger than 50 nanometers, giving this surface a relatively high roughness so as to allow mechanical attachment of the first matrix layer. By size of ceramic grains essentially between 20 nanometers and 200 nanometers is meant here that more than 80% of the ceramic grains have a size in this range. Moreover, the presence of grains larger than 50 nanometers should preferably be significant, that is to say represent at least 20% of the ceramic layer.

L'épaisseur moyenne de chaque première couche élémentaire d'interphase en carbone dopé au bore est de préférence comprise entre 20 nanomètres et 500 nanomètres.The average thickness of each first elemental layer of boron-doped carbon interphase is preferably between 20 nanometers and 500 nanometers.

L'épaisseur moyenne de chaque deuxième couche élémentaire d'interphase en carbure de silicium est de préférence comprise entre 20 nanomètres et 500 nanomètres.The average thickness of each second silicon carbide interphase elemental layer is preferably between 20 nanometers and 500 nanometers.

L'épaisseur totale moyenne du revêtement d'interphase est de préférence comprise entre 0,10 micromètres et 4 micromètres, en valeur moyenne.The average total thickness of the interphase coating is preferably between 0.10 micrometers and 4 micrometers, in average value.

On pourra choisir cette épaisseur totale de manière à assurer la consolidation de la préforme fibreuse par le seul revêtement d'interphase, c'est-à-dire avec un revêtement d'interphase liant entre elles les fibres de la préforme de façon suffisante pour avoir une préforme rigidifiée manipulable tout en conservant sa forme sans l'assistance d'un outillage de maintien.This total thickness can be chosen so as to ensure the consolidation of the fiber preform by the single interphase coating, that is to say with an interphase coating bonding together the fibers of the preform sufficiently to have a stiffened preform manipulated while retaining its shape without the assistance of a holding tool.

Avant formation du revêtement d'interphase et pour favoriser un bon accrochage de ce revêtement sur les fibres, la préforme fibreuse peut être traitée thermiquement comme décrit dans le document US 5 476 685 lorsqu'elle est en fibres de carbone ou être traitée chimiquement comme décrit dans le document US 5 071 679 , lorsqu'elle est en fibres de céramique, notamment en SiC ou essentiellement en SiC.Before forming the interphase coating and to promote a good attachment of this coating on the fibers, the fiber preform can be heat treated as described in document US 5,476,685 when it is made of carbon fiber or chemically treated as described in the document US 5,071,679 when it is made of ceramic fibers, in particular SiC or essentially SiC.

La préforme munie du revêtement d'interphase est ensuite densifiée par une matrice séquencée majoritairement en céramique comprenant des couches en céramique alternant avec des couches en matériau déviateur de fissures. Les couches en matériau déviateur de fissures peuvent être en carbone pyrolytique, éventuellement dopé au bore ou en nitrure de bore BN. Les couches en céramique peuvent être en SiC ou en un système ternaire Si-B-C ou en carbure de bore B4C. Pour les couches en céramique, on pourra alterner entre un matériau réfractaire tel que SiC et un matériau de type autocicatrisant tel que Si-B-C ou B4C. Par matériau autocicatrisant, on entend un matériau susceptible de générer une phase vitreuse par oxydation, réalisant ainsi une cicatrisation par comblement de fissure.The preform provided with the interphase coating is then densified by a predominantly ceramic sequenced matrix comprising ceramic layers alternating with layers of material deviating from cracks. The layers of crack-deflecting material may be made of pyrolytic carbon, optionally doped with boron or boron nitride BN. The ceramic layers may be SiC or a ternary system Si-BC or boron carbide B 4 C. For the ceramic layers, it is possible to alternate between a refractory material such as SiC and a self-healing type material such as Si -BC or B 4 C. Self-healing material means a material capable of generating a vitreous phase by oxidation, thus achieving healing by crack filling.

La matrice séquencée peut être obtenue par CVI. Des processus de réalisation de matrices séquencées sont décrits notamment dans les documents US 5 965 266 et US 6 068 930 déjà cités. Une matrice séquencée comprenant des couches en matériau céramique est particulièrement avantageuse en ce qu'en combinant un mode I de fissuration transversalement aux couches en céramique avec un mode II de fissuration parallèlement aux couches en matériau déviateur de fissure, elle retarde l'exposition du carbone de l'interphase à l'oxygène du milieu ambiant via le réseau de fissuration.The sequenced matrix can be obtained by CVI. Methods of producing sequenced matrices are described in particular in the documents US 5,965,266 and US 6,068,930 already mentioned. A sequential matrix comprising layers of ceramic material is particularly advantageous in that by combining a mode of cracking transverse to the ceramic layers with a mode of cracking parallel to the layers of material deflecting crack, it delays the exposure of the carbon from the interphase to the oxygen of the ambient medium via the cracking network.

La couche de matrice formée en premier (au plus près du revêtement d'interphase) est une couche en matériau déviateur de fissures PyC ou BC. La rugosité relativement forte de la surface externe de la couche élémentaire de revêtement d'interphase formée en dernier permet un accrochage mécanique entre le revêtement d'interphase et la matrice évitant avantageusement que sous l'effet de contraintes une décohésion se produise préférentiellement à ce niveau, créant un passage pour l'oxygène du milieu ambiant vers le carbone du revêtement d'interphase. En outre, de préférence, la résistance à la rupture en cisaillement de la première couche de la matrice en matériau déviateur de fissures est supérieure à celle existant par ailleurs au sein de la matrice.The matrix layer formed first (closest to the interphase coating) is a layer of PyC or BC crack deflector material. The relatively high roughness of the outer surface of the last formed interphase coating elemental layer allows a mechanical interlock between the interphase coating and the matrix advantageously avoiding that under the effect of constraints decohesion occurs preferentially at this level, creating a passage for oxygen from the ambient to the carbon of the interphase coating. In addition, preferably, the shear strength of the first layer of the crack-deflecting material matrix is greater than that otherwise existing within the matrix.

En complément avec le mode mixte de fissuration au sein de la matrice séquencée, cela contribue à améliorer la durée de vie du matériau CMC par préservation de l'intégrité de l'interphase. En outre, cet accrochage mécanique entre le revêtement d'interphase et la matrice contribue à assurer un bon transfert de charge de la matrice vers les fibres, ce qui est essentiel pour les propriétés mécaniques du matériau CMC.In addition to the mixed mode of cracking within the sequenced matrix, this contributes to improving the life of the CMC material by preserving the integrity of the interphase. In addition, this mechanical coupling between the interphase coating and the matrix contributes to ensuring a good charge transfer from the matrix to the fibers, which is essential for the mechanical properties of the CMC material.

Des exemples de réalisation de pièces en matériau CMC selon l'invention seront maintenant décrits ainsi que des exemples comparatifs.Examples of embodiments of CMC material parts according to the invention will now be described as well as comparative examples.

Exemple 1 (fibres C, interphase (BCpropane/SiC)x4, matrice type PyC, B4C, SiC, Si-B-C) (selon l'invention) Example 1 (C-fibers, interphase (BC propane / SiC) x4, PyC matrix-type, B 4 C, SiC, Si-BC) (Invention)

Des préformes fibreuses ont été obtenues à partir d'un tissu réalisé par tissage multicouches de fils de carbone. Le tissage a été effectué avec une armure de type interlock de manière à accroître la résistance au délaminage du matériau finalement obtenu. Des préformes ont été obtenues par découpe dans le tissu multicouches obtenu et maintien entre deux plaques perforées d'un conformateur en graphite, de manière à avoir un taux volumique de fibres généralement compris entre 30% et 50% environ (c'est-à-dire le pourcentage du volume apparent de la préforme occupé par les fibres).Fibrous preforms were obtained from a fabric made by multilayer weaving of carbon threads. The weaving was performed with interlock type weave so as to increase the delamination resistance of the finally obtained material. Preforms were obtained by cutting into the multilayer fabric obtained and held between two perforated plates of a graphite shaper, so as to have a volume content of fibers generally of between approximately 30% and 50% (i.e. say the percentage of the apparent volume of the preform occupied by the fibers).

Un revêtement d'interphase formé de couches de carbone pyrolytique dopé au bore alternant avec des couches de SiC a été réalisé par CVI classique sur les fibres des préformes. Le revêtement formé de 4 bi-couches BC/SiC est dénommé (BC/SiC)x4.An interphase coating formed of layers of boron-doped pyrolytic carbon alternating with SiC layers was made by conventional CVI on the fibers of the preforms. The coating formed of 4 bi-layers BC / SiC is called (BC / SiC) x4.

Le dépôt de chaque couche élémentaire de BC a été réalisé avec une phase gazeuse réactionnelle contenant un mélange de propane C3H8 et de trichlorure de bore BCl3 de manière à obtenir un matériau BC.The deposition of each elemental layer of BC was carried out with a gaseous reaction phase containing a mixture of C 3 H 8 propane and boron trichloride BCl 3 so as to obtain a BC material.

Le dépôt de chaque couche élémentaire de SiC a été réalisé avec une phase gazeuse réactionnelle contenant un mélange de MTS et H2.The deposition of each elemental layer of SiC was carried out with a reaction gas phase containing a mixture of MTS and H 2 .

Des processus de dépôt de couches BC et SiC par CVI sont décrits notamment dans le document précité US 6 068 930 .Processes for deposition of BC and SiC layers by CVI are described in particular in the aforementioned document US 6,068,930 .

Les paramètres de ces processus, notamment la durée de formation de chaque couche élémentaire ont été choisis pour obtenir des épaisseurs moyennes de l'ordre de 50 nanomètres et 100 nanomètres, respectivement pour les couches de BC et de SiC, donnant une épaisseur moyenne d'interphase consolidante de 0,6 micromètres environ. Il est toutefois à noter que ces épaisseurs varient fortement en fonction notamment de l'emplacement par rapport aux trous des plaques perforées du conformateur en graphite, la proximité d'un trou favorisant l'accès de la phase gazeuse réactionnelle, donc la formation d'une couche plus épaisse.The parameters of these processes, in particular the formation duration of each elemental layer, were chosen to obtain average thicknesses of the order of 50 nanometers and 100 nanometers, respectively for the BC and SiC layers, giving an average thickness of consolidating interphase of about 0.6 micrometers. It should however be noted that these thicknesses vary greatly depending in particular on the location relative to the holes of the perforated plates of the graphite shaper, the proximity of a hole favoring the access of the reaction gas phase, therefore the formation of a thicker layer.

Après formation du revêtement d'interphase, les préformes consolidées par ce revêtement ont été retirées de leur outillage de maintien et densifiées par CVI par une matrice majoritairement en céramique constituée de couches de carbone pyrolytique PyC alternant avec des couches de carbure de bore B4C ou de carbure de silicium SiC ou de carbure mixte de bore et de silicium formant un système ternaire Si-B-C, les couches formant ainsi la séquence suivante (en partant de la couche de matrice la plus proche de l'interphase) :
C/B4C/C/SiC/C/Si-B-C/C/SiC (qui peut être répétée une ou plusieurs fois)
les phases C en matériau déviateur de fissure étant en carbone pyrolytique issu de précurseur formé d'un mélange de propane et de gaz naturel,
les phases SiC en céramique réfractaire et les phases Si-B-C et B4C en céramique autocicatrisante étant obtenues comme décrit dans le document US 5 965 266 précité.
After formation of the interphase coating, the preforms consolidated by this coating were removed from their holding tool and densified by CVI by a predominantly ceramic matrix consisting of layers of pyrolytic carbon PyC alternating with layers of boron carbide B 4 C or silicon carbide SiC or mixed carbide boron and silicon forming a ternary system Si-BC, the layers thus forming the following sequence (starting from the matrix layer closest to the interphase):
C / B 4 C / C / SiC / C / Si-BC / C / SiC (which can be repeated one or more times)
the crack-deflecting material C phases being made of pyrolytic carbon derived from a precursor formed of a mixture of propane and natural gas,
the refractory ceramic SiC phases and the self-healing ceramics Si-BC and B 4 C phases being obtained as described in the document US 5,965,266 supra.

La rugosité de la surface externe de la couche de SiC de revêtement d'interphase formée en dernier apparaît sur les figures 1, 2 et 3 qui sont des vues au microscope du revêtement d'interphase au stade consolidation, avant poursuite de la densification, respectivement en coupe transversale, en coupe longitudinale et en surface. Cette rugosité vient de la formation de cette couche de SiC par des grains de taille moyenne relativement importante, ici supérieure à 50 nanomètres, donc avec présence significative de grains de taille supérieure à 50 nanomètres.The roughness of the outer surface of the last formed interphase coating SiC layer appears on the Figures 1, 2 and 3 which are microscopic views of the interphase coating in the consolidation stage, before further densification, respectively in cross section, in longitudinal section and at the surface. This roughness The formation of this SiC layer by grains of relatively large average size, here greater than 50 nanometers, thus with significant presence of grains larger than 50 nanometers.

Exemple 2 (fibres C, interphase (BCpropane/SiC)x4, matrice type BC, B4C, SiC, Si-B-C) (selon l'invention) Example 2 (C-fibers, interphase (BC propane / SiC) x4, BC type matrix, B 4 C, SiC, Si-BC) (according to the invention)

Il a été procédé comme dans l'exemple 1 sauf pour la matrice séquencée dans laquelle le carbone pyrolytique PyC des couches déviatrices de fissures est remplacé par du carbone dopé au bore BC de nature semblable à celui du revêtement d'interphase.The procedure was as in Example 1 except for the sequential matrix in which the PyC pyrolytic carbon of the deflector layers of cracks is replaced by BC boron-doped carbon of a nature similar to that of the interphase coating.

Exemple 3 (fibres C, interphase PyCCH4 /SiC, matrice type PyC, B4C, SiC, Si-B-C) (hors invention) Example 3 (C-fibers, PyC CH interphase 4 / SiC, matrix type PyC, B 4 C, SiC, Si-BC) (outside the invention)

Il a été procédé comme dans l'exemple 1 sauf pour le revêtement d'interphase qui était de type PyC/SiC formé d'une couche élémentaire de PyC recouverte d'une couche élémentaire de SiC. La couche élémentaire de PyC a été obtenue par CVI classique avec une phase gazeuse dans laquelle le précurseur de carbone était du gaz naturel, à savoir essentiellement du méthane. Les épaisseurs moyennes visées pour les couches de PyC et de SiC étaient respectivement de l'ordre de 100 nanomètres et 1 micron, suffisantes pour consolider les préformes.The procedure was as in Example 1 except for the interphase coating which was of PyC / SiC type formed of an elementary layer of PyC coated with an elemental layer of SiC. The elemental layer of PyC was obtained by conventional CVI with a gas phase in which the carbon precursor was natural gas, namely essentially methane. The average thicknesses targeted for the PyC and SiC layers were respectively of the order of 100 nanometers and 1 micron, sufficient to consolidate the preforms.

La figure 4 montre que la couche élémentaire de SiC présente en surface une rugosité relativement forte générée par la présence de grains de SiC grossiers de taille supérieure à 50.The figure 4 shows that the elementary layer of SiC has a relatively high surface roughness generated by the presence of coarse SiC grains larger than 50.

Exemple 4 (comparatif) (fibres C, interphase BC/B4C/BC/SiC, matrice type BC, B4C, SiC, Si-B-C) Example 4 (comparative) (C-fibers, BC / B 4 C / BC / SiC interphase, BC type matrix, B 4 C, SiC, Si-BC)

Il a été procédé comme dans l'exemple 2 sauf pour le revêtement d'interphase qui était de type BC/B4C/BC/SiC, les couches élémentaires de BC et la couche élémentaire de SiC étant obtenues comme dans l'exemple 2 et la couche élémentaire de B4C étant obtenue comme pour la matrice.The procedure was as in Example 2 except for the interphase coating which was of BC / B 4 C / BC / SiC type, the elementary layers of BC and the elementary layer of SiC being obtained as in Example 2 and the elementary layer of B 4 C being obtained as for the matrix.

La figure 5 montre que la surface externe de la couche SiC du revêtement d'interphase est relativement lisse.The figure 5 shows that the outer surface of the SiC layer of the interphase coating is relatively smooth.

Exemple 5 (comparatif) (fibres C, interphase (BCgaz nat/SiC)x4, matrice type BC, B4C, SiC, Si-B-C) Example 5 (comparative) (C-fibers, interphase (BC nat / SiC gas ) x4, BC type matrix, B 4 C, SiC, Si-BC)

Il a été procédé comme dans l'exemple 2 en remplaçant le précurseur de carbone pour les premières couches du revêtement d'interphase par du gaz naturel.The procedure was as in Example 2, replacing the carbon precursor for the first layers of the interphase coating with natural gas.

Les figures 6, 7 et 8 montrent que la couche de revêtement d'interphase formée en dernier (respectivement en coupe transversale, en coupe longitudinale et en surface) est formée de grains de SiC de dimension moyenne relativement faible et jointifs, ne conférant pas de rugosité significative.The Figures 6, 7 and 8 show that the interphase coating layer formed last (respectively in cross section, in longitudinal section and at the surface) is formed of SiC grains of relatively small average size and joined, not conferring significant roughness.

En comparant les figures 3 et 8 prises à la même échelle, on constate aisément la différence de taille des grains de SiC de la dernière couche de l'interphase. Par une analyse d'image appropriée on peut quantifier les tailles des grains.Comparing the figures 3 and 8 taken at the same scale, the difference in size of the SiC grains of the last layer of the interphase is easily observed. By appropriate image analysis it is possible to quantify grain sizes.

Exemple 6 (comparatif) (fibres C, interphase (PYCCH4 -C3H8 /SiC)x2, matrice type PyC, B4C, SiC, Si-B-C) Example 6 (Comparative) (C-fibers, interphase (PYC CH 4 - C 3 H 8 / SiC) x2, PyC matrix-type, B 4 C, SiC, Si-BC)

Il a été procédé comme dans l'exemple 3 sauf pour le revêtement d'interphase qui était de type (PyC/SiC) x 2 formé de deux couches de PyC alternant avec deux couches de SiC et avec des couches élémentaires de PyC obtenues par CVI classique avec une phase gazeuse dans laquelle le précurseur de PyC était un mélange de propane et de gaz naturel, le propane étant le principal précurseur.The procedure was as in Example 3 except for the interphase coating which was of the (PyC / SiC) x 2 type formed of two PyC layers alternating with two layers of SiC and with elementary layers of PyC obtained by CVI. conventional with a gas phase in which the PyC precursor was a mixture of propane and natural gas, propane being the main precursor.

L'épaisseur globale de l'interphase a été choisie de manière à être similaire à celle de l'exemple 3, suffisante pour consolider les préformes.The overall thickness of the interphase was chosen to be similar to that of Example 3, sufficient to consolidate the preforms.

La figure 9 montre que la couche élémentaire externe de PyC présente une faible rugosité, les grains de SiC étant de relativement petite dimension et jointifs.The figure 9 shows that the outer elemental layer of PyC has a low roughness, the SiC grains being of relatively small size and joined.

Essaistesting

Des pièces obtenues selon les exemples 1, 3 et 6 ont été soumises à des essais en traction. Les courbes A, B et C de la figure 10 montrent la relation entre contrainte en traction et allongement relatif pour des pièces des exemples 1, 3 et 6, respectivement, jusqu'à rupture. La forme linéaire de la courbe C sur sa plus grande partie, jusqu'à rupture, traduit une décohésion entre revêtement d'interphase et matrice, donc un plus faible transfert de charge entre matrice et fibres.Parts obtained according to Examples 1, 3 and 6 were subjected to tensile tests. Curves A, B and C of the figure 10 show the relationship between tensile stress and relative elongation for parts of Examples 1, 3 and 6, respectively, to failure. The linear shape of the curve C over most of it, until failure, reflects a decohesion between interphase coating and matrix, hence a lower charge transfer between matrix and fibers.

Des pièces obtenues selon les exemples 1, 3 et 6 ont également été soumises à des essais de durée de vie en fatigue cyclique à 600°C et 1200°C sous air, ces essais consistant à soumettre les pièces à une contrainte de traction de 120 MPa (en contrainte apparente) avec une fréquence de relaxation de la contrainte de 0,25 Hz.Parts obtained according to Examples 1, 3 and 6 were also subjected to cyclic fatigue life tests at 600 ° C. and 1200 ° C. in air, these tests consisting in subjecting the parts to a tensile stress of 120.degree. MPa (in apparent stress) with a stress relaxation frequency of 0.25 Hz.

Le tableau ci-après indique les résultats obtenus. Pièce Durée de vie à une température de : 600°C 1200°C Exemple 1 > 95 h 35 h Exemple 3 > 77 h 10 h Exemple 6 26 h 17 h The table below shows the results obtained. Piece Lifetime at a temperature of: 600 ° C 1200 ° C Example 1 > 95 h 35 h Example 3 > 77 h 10 am Example 6 26 h 17 h

La durée de vie des pièces obtenues selon les exemples 1 et 3 est bien supérieure à celle de la pièce obtenue selon l'exemple 6 à 600°C. A 1200°C, la durée de vie de la pièce obtenue selon l'exemple 3 est la plus faible, cela pouvant être expliqué par la plus grande sensibilité à l'oxydation du PyC obtenu à partir d'un précurseur gaz naturel.The service life of the parts obtained according to Examples 1 and 3 is much greater than that of the part obtained according to Example 6 at 600 ° C. At 1200 ° C, the service life of the part obtained according to Example 3 is the lowest, this being explained by the greater sensitivity to oxidation of PyC obtained from a natural gas precursor.

Des pièces obtenues selon les exemples 2 et 4 ont été soumises à des essais de durée de vie en fatigue cyclique à 600°C dans les mêmes conditions que celles indiquées ci-dessus.Parts obtained according to Examples 2 and 4 were subjected to cyclic fatigue life tests at 600 ° C. under the same conditions as those indicated above.

Le tableau ci-après indique les résultats obtenus. Pièce Durée de vie à 600°C Exemple 2 > 74 h Exemple 4 20 h The table below shows the results obtained. Piece Life at 600 ° C Example 2 > 74 h Example 4 8 pm

On constate à 600°C un meilleur comportement de la pièce de l'exemple 2 que de la pièce selon l'exemple 4, induisant qu'avec des premières couches élémentaires d'interphase en BC, la présence de plusieurs couches de SiC est préférable, la couche de B4C amorphe ne contribuant pas à de la génération de rugosité.At 600.degree. C., a better behavior of the part of Example 2 than of the part according to Example 4 is observed, inducing that, with first elementary layers of interphase in BC, the presence of several layers of SiC is preferable. , the amorphous B 4 C layer does not contribute to the roughness generation.

Des pièces selon les Exemples 2 et 5 ont été soumises à des essais de durée de vie en fatigue cyclique à 600°C dans les mêmes conditions que celles indiquées ci-dessus sauf pour la contrainte appliquée qui était de 90 MPa ou 130 MPa.Parts according to Examples 2 and 5 were subjected to cyclic fatigue life tests at 600 ° C under the same conditions as indicated above except for the applied stress which was 90 MPa or 130 MPa.

Le tableau ci-après indique les résultats obtenus. Pièce Durée de vie à 600°C pour une contrainte de : 90 MPa 130 MPa Exemple 2 > 500 h > 250 h Exemple 5 288 h, 383 h, > 500 h 87 h, 185 h The table below shows the results obtained. Piece Life at 600 ° C for a stress of: 90 MPa 130 MPa Example 2 > 500 h > 250 h Example 5 288 h, 383 h,> 500 h 87 h, 185 h

On constate une dispersion importante des résultats obtenus avec des pièces selon l'exemple 5, ces résultats étant globalement très sensiblement inférieurs à ceux obtenus avec des pièces selon l'exemple 2, la différence tenant au choix du précurseur de carbone pour les couches élémentaires d'interphase en BC, à savoir le gaz naturel (ou méthane) dans le premier cas et le propane dans le deuxième cas.There is a significant dispersion of the results obtained with parts according to Example 5, these results being overall very substantially lower than those obtained with parts according to Example 2, the difference relating to the choice of the carbon precursor for the elementary layers of interphase in BC, namely natural gas (or methane) in the first case and propane in the second case.

Les exemples qui précèdent montrent qu'une rugosité de surface de la couche élémentaire en céramique formée en dernier dans le revêtement d'interphase propre à assurer un accrochage mécanique efficace avec la matrice peut être obtenue en réalisant le revêtement d'interphase dans des conditions favorisant, dans cette dernière couche, une croissance des grains de céramique plutôt que leur germination, alors que des conditions favorisant la germination plutôt que la croissance génèrent des grains relativement petits et rapprochés dont la croissance est vite bloquée par leur proximité.The foregoing examples show that a surface roughness of the ceramic elemental layer formed last in the interphase coating capable of ensuring an effective mechanical coupling with the matrix can be obtained by performing the interphase coating under conditions favoring in this last layer, a growth of ceramic grains rather than their germination, then that conditions favoring germination rather than growth generate relatively small and close grains whose growth is quickly blocked by their proximity.

Claims (5)

  1. A part made of ceramic matrix composite material having fiber reinforcement of carbon or ceramic fibers and a majority-ceramic sequenced matrix having first matrix layers made of crack-deflector material alternating with second matrix layers made of ceramic material;
    • in which part an interphase coating is interposed between the fibers and the matrix, the interphase coating adhering to the fibers and to the matrix and being formed of at least one sequence constituted by a first elementary interphase layer made of carbon doped with boron surmounted by a second elementary interphase layer made of ceramic, the outer elementary layer of the interphase coating being a ceramic layer having an outer surface formed by ceramic grains of size lying essentially in the range 20 nm to 200 nm, with the presence of grains of size greater than 50 nm conferring roughness on the outer surface ensuring mechanical attachment with the adjacent matrix layer, the interphase coating being made of first elementary layers of boron-doped carbon alternating with second elementary layers of ceramic, and in each first elementary layer, the atomic percentage of boron lies in the range 5% to 20%, each second elementary layer of the interphase coating being made of silicon carbide, the matrix layer adjacent to the interphase coating is made of PyC or BC crack-deflector material.
  2. A part according to claim 1, wherein each first elementary layer of the interphase coating has mean thickness lying in the range 20 nm to 500 nm.
  3. A part according to any one of claim 1 or 2, wherein each second elementary layer of the interphase coating has mean thickness lying in the range 20 nm to 500 nm.
  4. A part according to any one of claims 1 to 3, wherein the total mean thickness of the interphase coating lies in the range 0.10 µm to 4 µm.
  5. A method of manufacturing a part according to any one of claims 1 to 4, the method comprising:
    - making a fiber preform made of carbon or ceramic fibers intended to constitute the fiber reinforcement of the part,
    - forming on the fibers of the preform, by isobaric chemical vapor infiltration, the interphase coating, the sequence being constituted by a first elementary layer made of pyrolytic carbon doped with boron surmounted by the second elementary layer, each first elementary layer of the interphase coating being formed from a gaseous phase wherein the carbon precursor is propane, and
    - densifying the fiber preform coated with the interphase coating by the majority-ceramic sequenced matrix.
EP12806552.1A 2011-12-13 2012-11-22 Part made of cmc Active EP2791080B1 (en)

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FR3025810B1 (en) * 2014-09-12 2016-12-09 Herakles PROCESS FOR PRODUCING A FIBROUS STRUCTURE
KR101743019B1 (en) * 2015-01-30 2017-06-05 한국과학기술연구원 High temperature oxidation resistant boron carbide thin film, cutting tools using the thin film and method of manufacturing the same
CN106968716B (en) * 2016-11-21 2017-12-19 北京航空航天大学 Ceramic matric composite turbine blisks
CN108316977B (en) * 2018-01-22 2019-01-22 北京航空航天大学 Multi-component multi-layer self-healing ceramic matric composite engine turbine outer ring
EP4008702A1 (en) 2020-12-03 2022-06-08 Raytheon Technologies Corporation Ceramic matrix composite with fibers having a specific coating
US20230047461A1 (en) * 2021-08-12 2023-02-16 Raytheon Technologies Corporation Particle based inserts for cmc

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CN104053638B (en) 2016-08-17
US20140363663A1 (en) 2014-12-11
US9604886B2 (en) 2017-03-28
FR2983851A1 (en) 2013-06-14
KR20140132705A (en) 2014-11-18
CN104053638A (en) 2014-09-17
JP2015500197A (en) 2015-01-05
WO2013088015A1 (en) 2013-06-20
EP2791080A1 (en) 2014-10-22
JP6301261B2 (en) 2018-03-28

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